Symmetrical secondary aliphatic polynitro diamines



wherein R and A are as identified above.

-' scope of the invention in any way SYMMETRICAL SECONDARY ALIPHATIC POLYNITRO DIAMINES Milton B. Frankel, Pasadena, and Karl Klager, Monrovia, Calif., assignors to Aerojet-General Corporation, Azusa, Califl, a corporation of Delaware No Drawing. Filed June 5, 1956, Ser. No. 589,559

12 Claims. (Cl. 260-583) This invention relates to new compositions of matter and a method for their preparation. In particular this invention relates to symmetrical polynitro diatnines having the general formula:

wherein R is a nitro or radical.

Due to their high oxygen content these compounds find valuable use as explosives.

alkyl radical and A'is an alkylene ice ' 2 EXAMPLE 1' Preparation of 1,1-,1,6,6,11,11,11-ctanitr0-4,8- i 1 diaza undecane To a solutionof 8.3 gm. (0.05 mole) of 2,2-dinitro-1,3-'

propanediol, 23.0'gm. (0.10 mole) of 3,3,3-trinitropropyl amine hydrochloride and 50 ml. of water was added a 7 solution of 88 ml. of 1.136 N sodium hydroxide (0.10

This application is a continuation in part of our copending US. patent application No. 419,616, filed March 29, 1954, now abandoned.

, The compounds of this invention are prepared by condensing geminal polynitro-containing amines V with 2,2- dinitro-1,3-propanediol, in accordance with. the general reaction scheme set forth below:

Optimum results wereobtained when the reaction was conducted at a pH of less than" about 8 and preferably from about 4 to 8. As a matter of convenience, itis preferred to generate the primary amine in situ. This may be accomplished by employing the mineral acid salt of the amine as the starting material and conducting the reaction in the presence of a base such. as the hydroxides or a lower alkanoic acid salt of an alkali or alkaline earth metal. Alternatively .the amine may be introduced into the reaction mixture as the amine salt of a weak organic acid which will hydrolyze to produce the free amine.

The amines used as starting materials in this invention are obtained by the reaction of a strong mineral acid upon the corresponding isocyanates which may be obtained by the reaction of a polynitro acyl halide upon sodium azide, as disclosed in assignees copending application No. 405,515, filed January 21, 1954, now Patent No 2,923,726.

To more fully illustrate our invention, the following examples are presented. .It should be understood, how-. 6

ever, that these examples are presented merely as a mole). A yellow solid precipitated. The product was collected, washed withwater and dried to give 21.7 gm. (88.8%) of a tan solid, M.P. -80 C., with decompo'a sition. The explosive values for this compound are as follows: 7

Lead block value 143 TNT= 100.

Ballistic mortarvalue 146 TNT=100.

EXAMPLE II Preparation of 2,2,7,7,12,12-hexanitro-5,9-

diaza tridecane 2,2,7,7,12,12-hexanitro-5,9-diaza tridecane was pre: pared by condensing 2,2-di'nitro-l,3-propanediol with 3,3 dinitrobutyl amine in accordance with the procedure described in Example I. The product wasobtainedin a 74.2% yield and exhibited a M.P.pf 110 (D -with decomposition. The explosive values of this compound areas follows: I

Lead block value 91 TNT-100.

Ballistic mortar value TNT= 100.

l We have also found that aminessuchas 4,4-dinitro-.

hexyl amine, 3,3-dinitroamyl amine .and -4,4,4-trinitrobutyl amine readily condense with 2,2-dinitro-1,3-propanediol to yield their corresponding polynitro diamines,

namely, 3,3,9,9,15,I5-hexanitro-7,1l diaza heptadecane,'

3,3,8,8,13,13-hexanitro-6,l0-diaza pentadecane and 1,1, l,7-,7,13,13-,13-octanitro-5,9-diaza tridecane.

It is apparent that any member of this series of mertical aliphatic polynitro diamines may bereadil'y pre;

pared by merely selecting the appropriate polyiiitro amine and condensing it with 2,2-dinit'ro-l,3-propanediol, in ac,- cordance with the teachings of this invention. g

The nitro compounds of this invention arefuseful as A high explosives and 'c'a'n'b'e used in any conventional explosive missile, projectile, rocket, or the like, as'the main explosive charge. Aniexample 'ofsuchamissile is "disclosedin United Stam -Patent No. 2,470,162,. issued May 17, 194-9. One way of using the high "explosives means of illustration and are not intended to limit the of this invention in a device such as that disclosedin United States Patent No. 2,470,162, is to' pack the crystalline explosive in powder form into the warhead of the missile Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufiiciently insensitive to withstand the'shock entailed l v in the ejection of a shell from a gunbarrel or from a i rocket launching tube under the pressure developed from i ignition of a propellant charge, and can be caused to ex? plode on operation of an impactor time fuse-mechanism,

firing a detonating explosive such as lead azide or mercury A fulminate.

We claim:

'1. As compositions of matter, symmetrical secondary aliphatic polynitro .diamines having the'general formula:

not No, No, Imp-ern-A-Nn-cng-p-cniNn-n cm-p n No, No, No;

wherein A is a lower alkylene radical and R is aradical, I

group consisting of nitro and-lower} Fatented Apr. 4, 1961 3. 2. As compositions of matter, symmetrical secondary aliphatic polynitro diamines having the general formula:

N: hIIOQ Nl'oi nor-c-cnr-a-Nn-cm-o-crrr-Nrr-A-care-No,

N0, N0, N0:

wherein A is a lower alkylene radical.

3. As compositions of matter, symmetrical secondary aliphatic polynitro diamines having the general formula:

1:10: N0, N0: R-(f-CHr-A-NEE-GHg-C-OHr-NH-A-OHr-'%R NO: NO: NO: wherein A is a lower alkylene radical and R is a lower aikyl radical.

r 4. As a composition of matter, 2,2,7,7,l2,12-hexanitro- 5,9-diaza tridecane having the structural formula:

5. As a composition of matter, l,1,1,6,6,11,11,11-

octa-nitro-4,8-diaza undecane having the structural formula:

N0 1 N 01 N 0 g NOa-(il-CHzCHq-NH-CHr-l-CHrNH-CHrCHz--NO:

I 01 I11 0 z 1110 6. The method of preparing symmetrical secondary aliphatic polynitro diamines having the general formula:

N01 IFO: N0: R-iI-CHr-A-NH-CHr-C-CHz-NH-A-CHz- R N01 NO: NO:

which comprises condensing 2,2-dinitro-1,3-propanediol with a polynitro-amine having the general formula:

No, Nor-r i-om-a-Nm wherein A is a lower alkylene radical.

9. The method of preparing symmetrical secondary aliphatic polynitro diamines having the general formula:

which comprises condensing 2,2-dinitro-1,3-propanediol with a polynitro-amine having the general formula:

No, R-(J-CHr-A-NH:

wherein A is a lower alkylene radical and R is a lower alkyl radical.

10. The method of preparing symmetrical secondary aliphatic polynitro diamines having the general formula:

which comprises condensing 2,2-dinitro-1,3-propanediol with a strong mineral acid salt of a primary polynitroamine having the general formula:

wherein A is a lower alkylene radical and R is a radical selected from the group consisting of lower alkyl and nitro radicals, in the presence of a base selected from the group consisting of the hydroxides of alkali and alkaline earth metals.

11. The method of preparing 2,2,7,7,12,12-hexanitro- 5,9-diaza tridecane which comprises condensing 3,3-dinitrobutyl amine hydrochloride with 2,2-dinitro-1,3-propanediol in the presence of sodium hydroxide.

12. The method of preparing 1,1,1,6,6,11,l1,11'octanitro-4,8diaza undecane which comprises condensing 3,3,3-trinitropropane amine hydrochloride with 2,2-dinitro-1,3-propanediol in the presence of sodium hydroxide. 4

No references cited. 

1. AS COMPOSITIONS OF MATTER, SYMMETRICAL SECONDARY ALIPHATIC POLYNITRO DIAMINES HAVING THE GENERAL FORMULA: 